JP4963825B2 - Polishing silica sol and polishing composition containing the same - Google Patents

Polishing silica sol and polishing composition containing the same Download PDF

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JP4963825B2
JP4963825B2 JP2005331807A JP2005331807A JP4963825B2 JP 4963825 B2 JP4963825 B2 JP 4963825B2 JP 2005331807 A JP2005331807 A JP 2005331807A JP 2005331807 A JP2005331807 A JP 2005331807A JP 4963825 B2 JP4963825 B2 JP 4963825B2
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silica sol
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JP2007137972A (en
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昭 中島
一昭 井上
修 吉田
祐一郎 田熊
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日揮触媒化成株式会社
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Description

  The present invention relates to an anisotropic shaped silica sol suitable as an abrasive and an efficient production method thereof.

In the manufacture of a substrate with a semiconductor integrated circuit, irregularities or steps are formed when forming a circuit with a metal such as copper on a silicon wafer. Removal is performed preferentially. Further, when an aluminum wiring is formed on a silicon wafer and an oxide film such as silica is provided thereon as an insulating film, irregularities due to the wiring are generated. Therefore, the oxide film is polished and flattened. In the polishing of such a substrate, the surface after polishing is required to be flat with no steps or irregularities, smooth without microscopic scratches, etc., and the polishing rate must be high.
Conventionally, silica sol, fumed silica, fumed alumina, or the like is used as the abrasive particles.

  The abrasive used in CMP is usually spherical abrasive particles having an average particle diameter of about 200 nm made of a metal oxide such as silica and alumina, and an oxidizer for increasing the polishing rate of the wiring / circuit metal. It is composed of additives such as organic acids and solvents such as pure water, but there are steps (unevenness) due to the groove pattern for wiring formed on the underlying insulating film on the surface of the material to be polished. It is required to polish the coplanar surface mainly while polishing and removing the convex portions to obtain a flat polished surface. However, with conventional spherical abrasive particles, when the portion above the coplanar surface is polished, the circuit metal in the wiring trench at the bottom of the recess is polished to below the coplanar surface (called dishing) There was.) If such dishing (overpolishing) occurs, the thickness of the wiring decreases and the wiring resistance increases, and the flatness of the insulating film formed thereon deteriorates. There is a need to suppress it.

  The abrasive containing the irregularly shaped particle group is such that, when polishing a substrate having such irregularities, polishing of the concave portion is suppressed until the upper end surface of the convex portion is at the same level as the bottom surface of the concave portion, and the upper end surface of the convex portion is concave. After polishing to the same level as the bottom surface, both the convex and concave portions can be polished at the same polishing rate, so dishing (overpolishing) does not occur, and the polished surface has no unevenness and is excellent in flatness. It has been. For example, since dishing does not occur during polishing in the formation of semiconductor integrated circuits, etc., without increasing the circuit resistance of the obtained integrated circuit, the surface after polishing is excellent in flatness, so that stacking can be performed efficiently. A circuit can be formed.

  In addition, the abrasives containing such irregularly shaped particles can be used for aluminum disks (aluminum or a plating layer on a base material thereof), aluminum wiring of semiconductor multilayer wiring boards, glass substrates for optical disks and magnetic disks, and liquid crystal displays. Application to glass substrates, glass substrates for photomasks, mirror finishing of glassy materials, and the like is expected.

As a method for producing the silica sol comprising irregular particles, the alkali metal silicate aqueous solution of 0.05 to 5.0 wt% as SiO 2 in JP-A 4-187512 (Patent Document 1), the mixture was added silicic acid solution SiO After 2 / M 2 O (molar ratio, M is alkali metal or quaternary ammonium) 30-60, Ca, Mg, Al, In, Ti, Zr, Sn, Si, Sb, Fe, Cu and rare earth A compound of one or two or more metals selected from the group consisting of metals is added (addition time may be before or during addition of the silicic acid solution), and this mixed solution is heated at an arbitrary temperature of 60 ° C. or higher. Disclosed is a method for producing a sol in which substantially irregularly shaped silica fine particles are dispersed in which a silicic acid solution is added and SiO 2 / M 2 O (molar ratio) in the reaction solution is set to 60 to 100 in a reaction solution. Yes.

In JP-A-7-118008 (Patent Document 2), an aqueous solution of a water-soluble calcium salt, magnesium salt or a mixture thereof is added to an aqueous colloidal solution of active silicic acid, and an alkaline substance is added to the resulting aqueous solution. A part of the obtained mixture is heated to 60 ° C. or more to obtain a heel liquid, the remainder is used as a feed liquid, the feed liquid is added to the heel liquid, and water is evaporated during the addition to evaporate SiO 2. A process for producing an elongated silica sol comprising concentrating to a concentration of 6-30% by weight is disclosed.

JP-A-2001-11433 (Patent Document 3) discloses a water-soluble II colloidal solution of active silicic acid containing 0.5 to 10% by weight of SiO 2 and having a pH of 2 to 6. an aqueous solution containing valence or III valent metal salt singly or as a mixture thereof, with respect to SiO 2 colloid solution having the same active silicic acid in the case of the metal oxide (II valent metal salt and MO, the III In the case of a metal salt of M 2 O 3 , M represents a II or III valent metal atom, and O represents an oxygen atom). Then, an acidic spherical silica sol having an average particle size of 10 to 120 nm and a pH of 2 to 6 is added to the obtained mixed liquid (1), and the silica content (A) derived from the acidic spherical silica sol and the mixed liquid (1). The ratio A / B (weight ratio) of silica content (B) is 5 to 100, and this acid Spherical silica sol and the mixture (1) and the resulting mixture by mixing (2) the total silica content (A + B) is added and mixed so that SiO 2 concentration of 5 to 40 wt% in the mixture (2) An alkali metal hydroxide or the like is added to and mixed with the mixed liquid (2) so that the pH becomes 7 to 11, and the obtained mixed liquid (3) is heated at 100 to 200 ° C. for 0.5 to 50 hours. A method for producing a beaded silica sol is described.

  Japanese Patent Laid-Open No. 2001-48520 (Patent Document 4) describes a composition having a silica concentration of 1 to 8 mol / liter, an acid concentration of 0.0018 to 0.18 mol / liter, and a water concentration of 2 to 30 mol / liter. The alkyl silicate is hydrolyzed with an acid catalyst without using a solvent, diluted with water so that the silica concentration is in the range of 0.2 to 1.5 mol / liter, and then the pH is 7 or more. An alkali catalyst is added and heated to advance the polymerization of silicic acid, and the average diameter in the thickness direction by electron microscope observation is 5 to 100 nm, and the length is 1.5 to 50 times that of a long and thin shape. A method for producing a silica sol in which crystalline silica particles are dispersed in a liquid dispersion is described.

JP 2001-150334 A (Patent Document 5) discloses an acidic aqueous solution of activated silicic acid having a SiO 2 concentration of about 2 to 6% by weight obtained by subjecting an aqueous solution of alkali metal silicate such as water glass to decation treatment. In addition, an alkaline earth metal such as a salt of Ca, Mg, Ba or the like is added in a weight ratio of 100 to 1500 ppm with respect to SiO 2 of the above active silicic acid in terms of its oxide, and further SiO 2 / M in this solution. 2 O (M represents an alkali metal atom, NH 4 or a quaternary ammonium group.) The liquid obtained by adding the same alkali substance in an amount that the molar ratio is 20 to 150 is the initial heel liquid. An active silicic acid aqueous solution having a SiO 2 concentration of 2 to 6% by weight and SiO 2 / M 2 O of 20 to 150 (M is the same as above) obtained as a charge liquid at 60 to 150 ° C. The charge liquid to the initial heel liquid per hour, In Yaji solution SiO 2 / initial 0.05-1.0 rate as the weight ratio of the heel solution SiO 2, (without or) a while evaporating off water from the liquid, method for producing a silica sol having a distorted shape obtained by adding the Are listed.

In JP-A-8-279480 (Patent Document 6), (1) a method in which an alkali silicate aqueous solution is neutralized with mineral acid, an alkaline substance is added and heat-aged, and (2) the alkali silicate aqueous solution is subjected to cation exchange treatment. A method of heating and aging by adding an alkaline substance to the obtained active silicic acid, (3) a method of heating and aging the active silicic acid obtained by hydrolyzing alkoxysilane such as ethyl silicate, or (4) fine silica powder Colloidal silica aqueous solution produced by, for example, a method of directly dispersing in an aqueous medium usually contains colloidal silica particles having a particle diameter of 4 to 1,000 nm (nanometer), preferably 7 to 500 nm. is obtained by dispersing 0.5 to 50% by weight SiO 2, preferably has a concentration of 0.5 to 30 wt%. It is described that the particle shape of the silica particles includes a spherical shape, a distorted shape, a flat shape, a plate shape, an elongated shape, and a fibrous shape.

  Japanese Patent Publication No. 2003-52962 (Patent Document 7) discloses an abrasive containing spherical, separated silica particles that are not connected to each other by a bond, and a) 5-95 weight silica particles having a size of 5-50 nm. And b) abrasives containing 95-5% by weight of silica particles of size 50-200 nm, but with the entire particle having a bimodal particle size distribution, are reported to give high polishing rates.

Japanese Patent Laid-Open No. 4-187512 Japanese Patent Laid-Open No. 7-118008 JP 2001-11433 A JP 2001-48520 A JP 2001-150334 A JP-A-8-279480 Japanese translation of PCT publication No. 2003-52962

An object of the present invention is to provide a polishing composition that exhibits excellent polishing properties for glass hard disks, quartz glass, quartz, aluminum disks, SiO 2 oxide films of semiconductor devices, silicon semiconductor wafers, compound semiconductor wafers, etc. There is to do. The present invention also provides a silica sol that is a main component of the polishing composition and a method for producing the same.

  1st invention of this application has the average particle diameter (D1) measured by the dynamic light scattering method in the range of 40-70 nm, and the average particle diameter (D2) measured by BET method is 10-50 nm. An anisotropic silica sol in which non-spherical silica fine particles having an irregularity (D1 / D2) in the range of 1.55 to 4.00 are dispersed, and dynamic light scattering of the anisotropic silica sol In the particle size distribution measured by the method, there is a particle size distribution peak in each of the particle size range A of 30 to 70 nm and the particle size range B of 71 to 150 nm (however, the absolute value of the difference in particle size corresponding to both peaks) Is in the range of 50 to 100 nm.), The ratio of the volume percent of particles present in the particle size range A to the volume percent of particles present in the particle size range B is 60:40 to 95: 5 Polishing characterized by being in range It is a silica sol.

  According to a second aspect of the present application, in the polishing silica sol, the particle size distribution peaks in each of a range of 30 to 50 nm in the particle size range A and a range of 90 to 130 nm in the particle size range B. There is a silica sol for polishing.

In the third invention of the present application, a silica hydrogel obtained by neutralizing a silicate with an acid is washed to remove salts, and after adding an alkali, the silica sol is heated to a range of 60 to 200 ° C. A method for producing a silica sol for polishing, characterized in that a silicic acid solution is continuously or intermittently added under the conditions of a temperature of 60 to 200 ° C. in a pH range of 9 to 12.5, using this as a seed sol. It is.
A fourth invention of the present application is the method for producing a polishing silica sol, wherein in the method for producing a polishing silica sol, the pH is adjusted to 9 to 12.5 by adding a pH adjusting agent to the seed sol. is there.

According to a fifth aspect of the present application, a silica sol for polishing is prepared by mixing an anisotropic shaped silica sol composed of a monodispersed phase having a particle size range A and an anisotropic shaped silica sol composed of a monodispersed phase having a particle size range B. It is the manufacturing method of the silica sol for grinding | polishing which obtains.
A sixth invention of the present application is a polishing composition containing the polishing silica sol.

According to the polishing composition containing the polishing silica sol according to the present invention, for example, an excellent polishing rate is achieved for a glass disk as compared with the case where a conventional polishing composition is used.
Moreover, according to the manufacturing method which concerns on this invention, the silica sol for polishing applied to the polishing composition of this invention can be manufactured efficiently.

Polishing silica sol The polishing silica sol of the present invention comprises an anisotropic shaped silica sol. Here, the anisotropic shaped silica sol is one in which the shape of the silica fine particles dispersed in the solvent is referred to as non-spherical, irregular, chained, beaded, wedged or elongated. Specifically, the average particle diameter (D1) measured by the dynamic light scattering method is in the range of 40 to 70 nm, the average particle diameter (D2) measured by the BET method is in the range of 10 to 50 nm, The degree of irregularity (D1 / D2) is in the range of 1.55 to 4.00.

When the average particle size (D1) measured by the dynamic light scattering method is less than 40 nm, the particle size of the silica fine particles is relatively small, so that the viscosity of the silica sol tends to be high, and there is a problem in storage. Further, even in polishing applications, sufficient polishing performance may not be exhibited. On the other hand, when the average particle diameter (D1) measured by the dynamic light scattering method exceeds 70 nm, it is difficult to exhibit sufficient polishing performance in polishing applications.
In addition, even when the average particle size (D2) measured by the BET method is less than 10 nm, the silica sol has a relatively high viscosity because the particle size of the silica fine particles is relatively small, and there is a problem in storage. Further, even in polishing applications, sufficient polishing performance may not be exhibited. When the average particle diameter (D2) measured by the BET method exceeds 50 nm, sufficient polishing performance is hardly exhibited in polishing applications.

The polishing silica sol of the present invention needs to have a degree of irregularity (D1 / D2) in the range of 1.55 to 4.00. The average particle size measured by the dynamic light scattering method tends to be a value influenced by the shape of the particle, particularly the major axis, whereas the average particle size measured by the BET method is measured. The value tends to be a measured value that is less affected by the shape of the particles. For this reason, when the silica fine particle is a true sphere, the value of the degree of deformation (D1 / D2), which is the ratio between the two, generally converges to 1, and the value tends to increase as the silica fine particle deviates from the true sphere. is there.
In the polishing silica sol of the present invention, if the degree of profile is less than 1.55, the contribution to the polishing effect as seen in the present invention is reduced. On the other hand, when the value of the irregularity exceeds 4.00, although the polishing effect is increased, problems such as generation of scratches increase, so that the practicality is lowered.

The polishing silica sol of the present invention is the above-mentioned anisotropic silica sol, wherein the particle size distribution measured by the dynamic light scattering method of the silica sol exhibits a so-called bimodal distribution. is there. Specifically, the bimodal particle size distribution has a particle size distribution peak in a particle size range A of 30 to 70 nm and a particle size range B of 71 to 150 nm, respectively (however, these correspond to both peaks). Only when the absolute value of the difference in particle size is in the range of 50 to 100 nm), the ratio of the volume percent of particles present in the particle size range A to the volume percent of particles present in the particle size range B is 60 : 40 to 95: 5. Here, the volume% of the particles existing in the particle diameter range A is the volume occupied by the silica fine particles corresponding to the particle diameter range A when the volume of the entire silica fine particles contained in the polishing silica sol of the present invention is 100%. Means the percentage of The same applies to the volume% of particles present in the particle diameter range B.
A polishing composition comprising such an anisotropic silica sol having the predetermined bimodal particle size distribution can exhibit an excellent polishing effect.

  In the polishing silica sol of the present invention, among the above-mentioned conditions, the ratio of the volume% of particles existing in the particle diameter range A to the volume% of particles existing in the particle diameter range B is 60:40 to 95. When the volume percentage of the particles existing in the particle diameter range A exceeds the upper limit of this range, the particle diameter range A is substantially close to the monodispersion of the particles existing in the particle diameter range A. Thus, the excellent polishing effect as seen in the polishing composition containing the polishing silica sol of the present invention cannot be obtained. On the other hand, when the volume% of the particles existing in the particle size range A is below the lower limit of this range, it is a bimodal particle size distribution, but can be seen in the polishing composition containing the polishing silica sol of the present invention. A superior polishing effect cannot be obtained.

  The absolute value of the difference in particle diameter corresponding to both peaks in the particle diameter ranges A and B needs to be in the range of 50 to 100 nm. When this value is less than 50 nm, the case where it is not substantially bimodal is included, and the effect of the invention cannot be achieved. On the other hand, when this value exceeds 100 nm, it is difficult to obtain the same effect as the present invention even if it has a bimodal particle size distribution.

In the polishing silica sol of the present invention, each peak in the particle size ranges A and B may be in the range of 30 to 50 nm in the particle size range A and in the range of 90 to 130 nm in the particle size range B. Recommended.
Regarding the ratio of the volume% of particles existing in the particle diameter range A to the volume% of particles existing in the particle diameter range B, a range of 70:30 to 90:10 is recommended.
The absolute value of the difference in particle size corresponding to both peaks in the particle size ranges A and B is preferably in the range of 53 to 80 nm, more preferably in the range of 53 to 70 nm.

Regarding the silica solid content concentration of the polishing silica sol of the present invention, those having a range of 1 to 50% by weight are usually used. The polishing silica sol having a silica solid content concentration in this range can be used practically as a raw material for the polishing composition. More preferably, a silica solid content concentration of 3 to 30% by weight is used. If the silica solid content concentration is less than 1% by weight, it is not suitable for efficient production of silica sol. On the other hand, when the silica solid content concentration exceeds 50% by weight, the stability of the silica sol is lowered, and it tends to aggregate.
The specific surface area of the polishing silica sol of the present invention is usually in the range of 60 to 700 m 2 / g.

The solvent for the polishing silica sol of the present invention may be either aqueous or non-aqueous, but when applied as a raw material for the polishing composition, a silica sol dispersed in an aqueous solvent is usually used. .
When the solvent of the polishing silica sol of the present invention is an aqueous solvent, the pH is mainly in the range of 9 to 12.5 in order to maintain the stability of the silica sol. If it is less than 9, the potential of the particles becomes small, so that the particles tend to aggregate and the tendency of the distribution to widen is increased. On the other hand, at 12.5 or more, the solubility of the particles increases, and the tendency that a part becomes an alkali silicate solution increases.

  Regarding the fact that the polishing composition containing the polishing silica sol of the present invention exhibits excellent polishing characteristics, as long as the tendency of the viscosity and polishing rate ratio of the polishing silica sol of the present invention is taken into consideration, the setting conditions of the present invention As a result of the coexistence of an anisotropic shaped silica sol having a large particle size and an anisotropic shaped silica sol having a small particle size at a relatively low viscosity, large particles and small particles contribute to polishing efficiently during polishing. Inferred.

Manufacturing method of polishing silica sol The manufacturing method of the polishing silica sol according to the present invention is not particularly limited as long as a silica sol satisfying the above requirements of the polishing silica sol of the present invention is finally obtained. 1) A silica sol is prepared by a peptization method, and particles are grown as needed. (2) A silica sol composed of a plurality of non-spherical silica fine particles monodispersed in a range where the particle diameter ranges do not overlap is mixed. The method etc. can be mentioned.

(1) First production method The peptization method usually involves neutralizing an aqueous silicate solution with an acid to prepare a silica hydrogel, and slurrying the silica hydrogel by chemical means or mechanical means. Means a method of forming a dispersion or solution. Here, as a chemical means, the method of adding an alkali to a silica hydrogel and heating as desired is mentioned. Moreover, as a mechanical means, the method of using apparatuses, such as a stirrer, can be mentioned. These chemical means and mechanical means may be used in combination.

As a preferred method for producing the polishing silica sol of the present invention, there can be mentioned a production method in which a silica sol prepared by such a peptization method is grown as necessary.
Specifically, silica hydrogel obtained by neutralizing silicate with acid is washed, salts are removed, alkali is added, and the silica hydrogel is peptized by heating in the range of 60 to 200 ° C. Then, a silica sol is prepared. Then, this is used as a seed sol, an alkali is added as necessary, the pH is adjusted to 9 to 12.5, and the silicic acid solution is added continuously or intermittently at a temperature of 60 to 200 ° C. A silica sol is prepared.

The silicate used as a raw material in this production method is preferably one or more silicates selected from alkali metal silicates, ammonium silicates, and organic base silicates.
Examples of the alkali metal silicate include sodium silicate (water glass) and potassium silicate, and examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, amines such as monoethanolamine, diethanolamine, and triethanolamine. In addition, the ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound, or the like to a silicic acid solution.

In the method for producing a polishing silica sol according to the present invention, an aqueous solution of silicate is prepared and neutralized with an acid to prepare a hydrogel. The concentration of the silicate aqueous solution is preferably 1 to 10% by weight, more preferably 2 to 8% by weight as SiO 2 .
When this concentration is less than 1% by weight as SiO 2 , the polymerization (gelation) of silicic acid is insufficient, and it is not easy to obtain a hydrogel under practical conditions. On the other hand, when this concentration exceeds 10% by weight as SiO 2 , neutralization cannot be performed uniformly, and the polymerization of silicic acid becomes non-uniform, and the variation in the size of the anisotropically shaped silica sol finally obtained increases.

The pH after neutralization is preferably in the range of 3-7. When the pH after neutralization is 3 to 7, it is easy to obtain a uniform hydrogel. When the pH is less than 3, the hydrogel structure is weak, and silica is easily eluted from the filter cloth during washing. When exceeding, there exists a fault that a part siloxane bond occurs and it is difficult to peptize. As the acid used for neutralization, hydrochloric acid, nitric acid, sulfuric acid and the like are used.
Thus, after neutralizing with an acid, it is preferably aged by standing at 15 to 35 ° C. for about 10 hours at the maximum. Regarding the aging time, a range of 10 minutes to 3 hours is usually recommended.

The silica hydrogel obtained by neutralization in this way is washed for the purpose of mainly removing salts generated by neutralization. Usually, it is washed with pure water or ammonia water using a filter such as an Oliver filter. For example, when sodium sulfate is produced, the concentration of sodium sulfate after washing is desirably 0.05% or less with respect to the solid content of SiO 2 , and the smaller the amount, the shorter the peptization time. If the salt concentration is high, the negative potential of the sol particles is small and agglomerates are easily formed even when peptized, so that a stable sol solution cannot be obtained.

  An alkali is added to the silica hydrogel which has been washed to pept the silica hydrogel. Usually, water is added to silica hydrogel and a silica hydrogel dispersion is prepared in a fluid slurry state with a strong stirrer. A moderate amount of alkali is added to the silica hydrogel dispersion, and the mixture is further stirred to peptize the silica hydrogel. The method is taken.

As the alkali, alkali metal hydroxides such as KOH and NaOH, ammonium hydroxide, and an aqueous amine solution can be used.
The amount of alkali used is preferably added so that the pH is 5-11. If the pH is less than 5, the dispersion becomes highly viscous, making it difficult to obtain a stable silica sol. When it exceeds pH 11, silica is easily dissolved and becomes unstable.

  The temperature at which the silica hydrogel is peptized with an alkali is preferably in the range of 60 to 200 ° C, more preferably 70 to 170 ° C. When the temperature is lower than 60 ° C., sufficiently uniform peptization may not be possible. When the temperature exceeds 200 ° C., the particle size of the silica sol obtained tends to be spherical. After the alkali is added to the silica hydrogel, the silica hydrogel is peptized by stirring in a temperature range of 60 to 200 ° C., usually for about 10 minutes to 3 hours.

At this time, the concentration of the silica hydrogel dispersion is preferably in the range of 0.5 to 10 wt%, more preferably 3 to 7 wt% as SiO 2 . When this concentration is less than 0.5% by weight, the ratio of dissolved silica increases, and the average particle size of the silica fine particles obtained decreases, so that the particle growth rate during the particle growth performed in the next step is remarkably high. Tends to slow down. On the other hand, if this concentration exceeds 10% by weight as SiO 2 , the average particle diameter of silica fine particles obtained by peptization tends to be non-uniform.
In addition, for the purpose of stabilizing the silica sol after peptization, it may be allowed to stand at a temperature of 60 to 200 ° C. for 10 minutes to 3 hours.

The silica sol obtained by peptization is used as a seed sol, and a silica sol composed of non-spherical silica fine particles is prepared by continuously or intermittently adding a silicic acid solution in the range of 60 to 200 ° C.
For the seed sol, if necessary, dilution with pure water and addition of alkali or silicate are performed, and the silica solid content concentration is preferably adjusted to 1 to 10% by weight, and the pH is adjusted to the range of 9 to 12.5. . When the pH is less than 9, the electric potential of the particles becomes small, the particles tend to aggregate and the particle size distribution tends to spread. If it exceeds 12.5, the solubility of the particles increases, so that the tendency to inhibit the growth of the particles becomes strong.

  The type of alkali is not particularly limited, but alkali metal hydroxides such as KOH and NaOH, ammonium hydroxide, aqueous amine solution, aqueous ammonia and the like are used. Although the silicate is not particularly limited, a silicate as exemplified above can be used. Preferably, it is recommended to use sodium silicate, potassium silicate or the like in the form of an aqueous solution. After adding the alkali or silicate, stir well.

Next, silica fine particles are grown by continuously or intermittently adding a silicic acid solution while maintaining the temperature of the seed sol in the range of 60 to 200 ° C. About the addition amount of a silicic acid liquid, it adjusts according to the magnitude | size of the particle diameter of the desired nonspherical silica fine particle.
When the temperature of the seed sol is less than 60 ° C., the dissolution rate of silicic acid in the seed sol to which the silicic acid solution is added, the deposition rate of silica on the seed, and the like become slow. On the other hand, if the temperature of the seed sol is higher than 200 ° C., it is advantageous because the dissolution rate and precipitation rate described above can be increased, but it is not only difficult to control the particle diameter and particle shape. This is not preferable because it is an expensive process. About the temperature at the time of adding a silicic acid liquid continuously or intermittently, the range of 60-100 degreeC is recommended suitably.

  Here, even when the silicic acid solution is continuously added or when the silicic acid solution is intermittently added, the silicic acid solution is gradually added to grow the silica fine particles. Specifically, in any of the above cases, it is recommended to add it preferably over 30 minutes to 72 hours.

  Here, as a silica sol obtained by peptization used as a seed sol, a silica sol having an average particle diameter of 5 to 30 nm measured by a BET method is preferably used. When a silica sol in this range is used as a seed sol, it tends to be a silica sol having an average particle diameter measured by the BET method in the range of 10 to 150 nm after particle growth. In addition, in order to use the seed sol having an average particle diameter in the above range, the silica sol obtained by peptization may be selected by a centrifugal separator, if desired.

As for the silicic acid solution used here, desirably, a silicic acid solution obtained by dealkalizing an alkali silicate salt is used. Such a silicic acid solution is a low polymer solution of silicic acid obtained by removing an alkali by treating an aqueous solution of an alkali silicate salt with a cation exchange resin, and is generally also called an acidic silicic acid solution. . Usually, a silicic acid solution having a SiO 2 concentration of 1 to 10% by weight is used.
As the silicate alkali salt, for example, any of sodium silicate, potassium silicate, lithium silicate, quaternary ammonium silicate, etc. can be used, preferably No. 1 water glass, No. 2 water glass, No. 3 water glass, etc. Sodium silicate or potassium silicate marketed by name is selected. In addition, an alkali silicate aqueous solution obtained by hydrolyzing a hydrolyzable organic compound such as tetraethylorthosilicate (TEOS) using excess NaOH or the like is also suitable.

  When adding the silicic acid solution, a new seed must not be generated. For this reason, the addition rate of the silicic acid solution into the seed solution has a great influence on the particle size, particle size distribution, and shape of the silica fine particles of the final product. In the production method of the present invention, it is desirable to add the silicic acid solution continuously or intermittently over 30 minutes to 72 hours. Thereby, a silica sol composed of non-spherical silica fine particles can be obtained.

  As for the polishing silica sol of the present invention, the silica sol prepared by the peptization method has an average particle diameter (D1) measured by the dynamic light scattering method in the range of 40 to 70 nm, and measured by the BET method. An anisotropic silica sol in which non-spherical silica fine particles having an average particle diameter (D2) in the range of 10 to 50 nm and an irregularity (D1 / D2) in the range of 1.55 to 4.00 are dispersed. In the particle size distribution measured by the dynamic light scattering method of the anisotropic shaped silica sol, there is a particle size distribution peak in each of the particle size range A of 30 to 70 nm and the particle size range B of 71 to 150 nm (however, The absolute value of the difference in particle diameter corresponding to both peaks is in the range of 50 to 100 nm), the volume% of particles present in the particle diameter range A and the volume% of particles present in the particle diameter range B The ratio of 0: 40 to 95: when in the range of 5, without grain growth, can be used as a polishing silica sol of the present invention.

(2) Second Production Method Another method for producing the polishing silica sol according to the present invention includes an anisotropic silica sol showing a monodisperse phase in the particle size range A and a different shape showing a monodisperse phase in the particle size range B. It is also possible to prepare a polishing silica sol that satisfies the above-mentioned conditions by mixing with a rectangular silica sol. Centrifugation may be used in combination for the purpose of adjusting the particle size distribution.

The silica sol composed of non-spherical silica fine particles obtained by the production method of the present invention can be converted into an organosol by replacing water as a dispersion medium with an organic solvent by a known method such as vacuum distillation or ultrafiltration. is there.
As such an organic solvent, solvents such as alcohols, glycols, esters, ketones, nitrogen compounds, and aromatics can be used. Specifically, methanol, ethanol, propanol, ethylene glycol, and the like can be used. And organic solvents such as propylene glycol, glycerin, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, dimethylformamide, and N-methyl-2-pyrrolidone.
Further, a polymer compound such as polyethylene glycol and silicone oil can be used as a dispersion medium.

Polishing Composition The polishing silica sol of the present invention is blended as a component of the polishing composition and exhibits an excellent polishing effect. The polishing silica sol of the present invention includes an aluminum disk (aluminum or a plating layer on a substrate thereof), an aluminum wiring of a semiconductor multilayer wiring board, an optical disk, a glass substrate for a magnetic disk, a glass substrate for a liquid crystal display, a glass substrate for a photomask, It can be used as a component of a polishing composition applied to polishing applications such as mirror finishing of glassy materials.

The composition of the polishing composition is prepared by concentrating or diluting the polishing silica sol (aqueous system) of the present invention, further blending other components as necessary, and making it into a slurry if desired. Here, examples of other components added to the polishing silica sol include polishing accelerators, surfactants, buffers, stabilizers, and aqueous media. An abrasive other than the polishing silica sol of the present invention may be used in combination.
Examples of other components used together with the polishing silica sol of the present invention in the polishing composition of the present invention are listed below, but are not limited thereto.

In the case of a polishing composition intended for silicon wafers, aluminum disks, glass disks, etc., as the other components, as a polishing accelerator, in the alkaline system, metal hydroxides such as potassium hydroxide and sodium hydroxide, Metal oxides such as sodium carbonate and ammonium carbonate, amines such as ammonia, monoethanolamine and piperazine, quaternary ammonium hydroxides such as tetramethylammonium, etc. In the oxide system, hydrogen peroxide, chlorine compounds, etc. Can be mentioned.
As the surfactant, anionic, cationic, nonionic or amphoteric surfactants can be used.

  As ions used as a buffering agent, although depending on the pH range to be adjusted, the cation is at least one of quaternary ammonium ion and alkali metal ion, and the anion is carbonate ion, bicarbonate ion, boron. It is preferable that it is at least 1 type or more of an acid ion and phenol. Particularly preferred are a mixture of carbonate ions and bicarbonate ions, borate ions, and the like.

Examples of the stabilizer include celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose, water-soluble polymers such as polyvinyl alcohol, water-soluble alcohols such as ethanol, ethylene glycol, propylene glycol and glycerin, and sodium alkylbenzene sulfonate. Examples thereof include surfactants, organic polyanionic substances such as polyacrylates, inorganic salts such as magnesium chloride and potassium acetate.
The SiO 2 concentration in the polishing composition is usually 3 to 20% by weight, but is not necessarily limited to this range.

[Preparation of silica sol for polishing]
A sodium silicate aqueous solution having a SiO 2 concentration of 24% by weight (SiO 2 / Na 2 O molar ratio: 3.1) 33.4 g was diluted with 126.6 Kg of pure water to obtain a sodium silicate aqueous solution having a SiO 2 concentration of 5% by weight. 160 kg of (pH 11) was prepared. The aqueous solution of sodium silicate was neutralized by adding an aqueous sulfuric acid solution having a sulfuric acid concentration of 25% so that the pH of the aqueous solution of sodium silicate was 4.5, and was aged by maintaining at room temperature for 5 hours to prepare a silica hydrogel. (Hereinafter, “%” means “% by weight” unless otherwise specified.)
This silica hydrogel was sufficiently washed with pure water (an amount equivalent to about 120 times the SiO 2 solid content) using a filter with a filter cloth, to remove salts contained in the silica hydrogel. The concentration of sodium sulfate in the silica hydrogel after washing was less than 0.01% by weight based on the SiO 2 solid content of the silica hydrogel.

This silica hydrogel was dispersed in pure water to prepare a dispersion having a SiO 2 concentration of 3% by weight, and the mixture was stirred using a powerful stirrer until a fluid slurry was obtained.
Ammonia water having a concentration of 15% was added so that the pH of the slurry-like silica hydrogel dispersion was 10.5, and stirring was continued at 95 ° C. for 1 hour to perform a peptization operation of the silica hydrogel. Obtained.

After the obtained silica sol was stabilized by heating at 150 ° C. for 1 hour, the silica sol was made to have an SiO 2 concentration of 13% by weight using an ultrafiltration membrane (product number: SIP-1013, manufactured by Asahi Kasei Corporation). Concentrated to Next, after concentrating to 30% by weight with a rotary evaporator, it was filtered with a 44 μm mesh nylon filter.
The viscosity of the obtained silica sol was 6.3 mPa · s, the specific surface area of the silica fine particles was 164 m 2 / g, and the average particle diameter (D2) determined from the specific surface area by the BET method was 17 nm. Moreover, the average particle diameter (D1) measured by the dynamic light scattering method was 44 nm, and the value of the degree of irregularity (D1 / D2) was 2.59.

For the particles in which this silica sol is present in each of the particle size range A (30 to 70 nm) and the particle size range B (71 to 150 nm), the average particle size and volume% at the peak position were measured.
Moreover, the apparatus shown below was used for the measurement of the average particle diameter of this silica sol, a specific surface area, a zeta potential, and a particle size distribution.

・ Particle size distribution measuring instrument: manufactured by Particle Sizing Systems, NICOMP-380 / ZLS
・ Zeta potential measuring device: Malvern, Zetasizer 3000HS
・ Optical microscope Olympus Corporation, MX50
Specific surface area: A specific surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisoap 12) was prepared for a sample prepared by adjusting 50 ml of sol to pH 3.5 with HNO 3 , adding 40 ml of n-propyl alcohol and drying at 110 ° C. for 20 hours. And measured by a nitrogen adsorption method (BET method).

[Polishing property test]
Preparation of polishing slurry A 5% aqueous sodium hydroxide solution and ultrapure water were added to the polishing silica sol having a silica concentration of 20% by weight obtained in Example 1 to prepare a polishing slurry having a silica concentration of 9% by weight and pH 10.5. did.
Polished substrate A glass substrate for hard disk made of 65 mmφ tempered glass was used as the substrate to be polished. This glass substrate for hard disk has been subjected to primary polishing and has a maximum surface roughness of 0.21 μm.

Polishing test The substrate to be polished is set in a polishing apparatus (NF300 manufactured by Nano Factor Co., Ltd.), and “Apollon” manufactured by Rodel is used as a polishing pad, and polished at a substrate load of 0.18 MPa and a table rotation speed of 30 rpm. Polishing was performed by supplying the slurry for 10 minutes at a rate of 20 g / min.
The polishing rate was calculated by determining the weight change of the substrate to be polished before and after polishing. The ratio of the polishing rate when the polishing rate in Comparative Example 4 described later was 1 was defined as the polishing rate.

Further, the polished surface was observed, the smoothness of the surface was observed with an optical microscope, and the following criteria were evaluated.
A: No scratch was observed.
B: Small scratches were slightly observed.
C: Small scratches were widely recognized.
D: Large scratches were observed.

The measured values obtained above are shown in [Table 1] and [Table 2]. Also, in Examples 2 to 5 and Comparative Examples 1 to 7 shown below, polishing slurries were similarly prepared, and polishing characteristic tests were performed.

To 6.7 kg of silica sol finally obtained in Example 1, 65.1 kg of pure water and 0.5 kg of 24 wt% sodium silicate aqueous solution were added and stirred at room temperature for 10 minutes to obtain a seed sol. This seed sol (72.3 Kg) had a SiO 2 concentration of 2.9% by weight and an average particle size (D2) measured by the BET method of 17 nm.
Next, this seed sol was maintained at 83 ° C., and 117 kg of silicic acid solution having a SiO 2 concentration of 3.0% by weight was added thereto over 14 hours to grow particles. After completion of the addition, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 20% by weight with an ultrafiltration membrane.

The resulting silica sol had a viscosity of 2.8 mPa · s, a specific surface area of 116 m 2 / g, and an average particle diameter (D2) determined from the specific surface area by the BET method was 24 nm. Moreover, the average particle diameter (D1) measured by the dynamic light scattering method was 47 nm. The value of (D1 / D2) was 1.96.

To 2.4 kg of silica sol obtained in Example 1, 12.1 kg of pure water and 0.8 kg of 24 wt% sodium silicate aqueous solution were added and stirred at room temperature for 10 minutes to obtain a seed sol. This seed sol (15.3 Kg) had a SiO 2 concentration of 5.0% by weight and an average particle size (D2) measured by the BET method of 17 nm.
Next, while maintaining the seed sol at 87 ° C., 173 kg of a silicic acid solution having a SiO 2 concentration of 3.0% by weight was added thereto over 14 hours to grow particles. After completion of the addition, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 20% by weight with an ultrafiltration membrane.
The obtained silica sol had a viscosity of 2.1 mPa · s, a specific surface area of 87 m 2 / g, and an average particle diameter (D2) determined from the specific surface area by the BET method was 31 nm. Moreover, the average particle diameter (D1) measured by the dynamic light scattering method was 50 nm. The value of (D1 / D2) was 1.6.

10.8 kg of pure water and 0.8 kg of a 24 wt% aqueous sodium silicate solution were added to 2.1 kg of the silica sol obtained in Example 1, and the mixture was stirred at room temperature for 10 minutes to obtain a seed sol. The seed sol (13.7 Kg) had a SiO 2 concentration of 4.9% by weight and an average particle size (D2) measured by the BET method of 17 nm.
Next, while maintaining the seed sol at 87 ° C., 176 kg of a silicic acid solution having a SiO 2 concentration of 3.0% by weight was added thereto over 14 hours to grow particles. After completion of the addition, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 20% by weight with an ultrafiltration membrane.
The resulting silica sol had a viscosity of 2.1 mPa · s, a specific surface area of 84 m 2 / g, and an average particle diameter (D2) determined from the specific surface area by the BET method was 33 nm. Moreover, the average particle diameter (D1) measured by the dynamic light scattering method was 54 nm. The value of (D1 / D2) was 1.6.

To 1 kg of the silica sol obtained in Example 1, 17.0 kg of pure water and 0.9 kg of a 24 wt% sodium silicate aqueous solution were added and stirred at room temperature for 10 minutes to obtain a seed sol. The seed sol (18.9 Kg) had a SiO 2 concentration of 1.8% by weight and an average particle size (D2) measured by the BET method of 17 nm.
Next, while maintaining the seed sol at 87 ° C., 176 kg of a silicic acid solution having a SiO 2 concentration of 3.2 wt% described later was added over 14 hours to grow particles. After completion of the addition, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 20% by weight with an ultrafiltration membrane.
The resulting silica sol had a viscosity of 2.0 mPa · s, a specific surface area of 73 m 2 / g, and an average particle diameter (D2) determined from the specific surface area by the BET method was 37 nm. Moreover, the average particle diameter (D1) measured by the dynamic light scattering method was 59 nm. The value of (D1 / D2) was 1.6.

Comparative Example 1

56.3 kg of pure water and 0.9 kg of a 24 wt% sodium silicate aqueous solution were added to 6.9 kg of the silica sol obtained in Example 3, and stirred at room temperature for 10 minutes to obtain a seed sol. The seed sol (64.1 Kg) had a SiO 2 concentration of 3.2% by weight and an average particle size (D2) measured by the BET method of 31 nm.
Next, while maintaining the seed sol at 98 ° C., 117 kg of a silicic acid solution having a SiO 2 concentration of 4.7% by weight was added thereto over 5 hours to grow particles. After completion of the addition, the mixture was cooled to room temperature, and the obtained silica sol was concentrated to an SiO 2 concentration of 20% by weight with an ultrafiltration membrane.
The obtained silica sol had a viscosity of 1.8 mPa · s, a specific surface area of 61 m 2 / g, and an average particle diameter (D2) determined from the specific surface area by the BET method was 45 nm. Moreover, the average particle diameter (D1) measured by the dynamic light scattering method was 65 nm. The value of (D1 / D2) was 1.4.

Comparative Example 2

About silica sol A (trade name: Cataloid PPS-50Y [average particle diameter (D2) measured by BET method: 25 nm, manufactured by Catalyst Kasei Kogyo Co., Ltd.]) having a particle size distribution of a monodisperse phase, as in Comparative Example 1. Measurements were made.

Comparative Example 3

About silica sol B (trade name: Cataloid SI-45P [average particle diameter (D2) measured by BET method: 45 nm, manufactured by Catalyst Chemical Industry Co., Ltd.]) having a particle size distribution of a monodisperse phase, as in Comparative Example 1. Measurements were made.

Comparative Example 4

About silica sol C (trade name: Cataloid SI-80P [average particle diameter (D2) measured by BET method: 80 nm, manufactured by Catalyst Kasei Kogyo Co., Ltd.]) having a particle size distribution of a monodisperse phase, as in Comparative Example 1. Measurements were made.

Comparative Example 5

A spherical silica sol having an average particle diameter of 41 nm measured by a dynamic light scattering method and a spherical silica sol having an average particle diameter of 111 nm were mixed at a volume ratio of 60:40. The mixed silica sol was measured in the same manner as in Comparative Example 1.

Comparative Example 6

Silica sol A of Comparative Example 2 and Silica sol C of Comparative Example 4 were mixed at a volume ratio of 74:26. The mixed silica sol was measured in the same manner as in Comparative Example 1.

Comparative Example 7

  Silica sol B of Comparative Example 3 and Silica sol C of Comparative Example 4 were mixed at a volume ratio of 60:40. The mixed silica sol was measured in the same manner as in Comparative Example 1.

Claims (6)

  1. The average particle size (D1) measured by the dynamic light scattering method is in the range of 40 to 70 nm, the average particle size (D2) measured by the BET method is in the range of 10 to 50 nm, and the degree of irregularity (D1 / D2) is an anisotropic silica sol in which non-spherical silica fine particles having a range of 1.55 to 4.00 are dispersed, and the particle size distribution measured by the dynamic light scattering method of the anisotropic silica sol There is a particle size distribution peak in each of the particle size range A of 30 to 70 nm and the particle size range B of 71 to 150 nm (provided that the absolute value of the difference in particle size corresponding to both peaks is in the range of 50 to 100 nm) The polishing is characterized in that the ratio of the volume% of the particles existing in the particle diameter range A to the volume% of the particles existing in the particle diameter range B is in the range of 60:40 to 95: 5. Silica sol for use.
  2. 2. The silica sol for polishing according to claim 1, wherein there is a peak of particle size distribution in each of a range of 30 to 50 nm in the particle size range A and a range of 90 to 130 nm in the particle size range B. .
  3. Silica hydrogel obtained by neutralizing silicate with acid is washed to remove salts, and after adding alkali, it is heated to a range of 60 to 200 ° C. to prepare a silica sol. The method for producing a silica sol for polishing according to claim 1 or 2, wherein the silicic acid solution is continuously or intermittently added in a range of -12.5 in a temperature range of 60-200 ° C. .
  4. The method for producing a polishing silica sol according to claim 3, wherein the pH is adjusted to 9 to 12.5 by adding a pH adjusting agent to the seed sol.
  5. 3. The polishing silica sol according to claim 1, wherein the anisotropic silica sol composed of a monodispersed phase having a particle size range A and the anisotropic silica sol composed of a monodispersed phase having a particle size range B are mixed. The manufacturing method of the silica sol for grinding | polishing which obtains.
  6. A polishing composition comprising the polishing silica sol according to claim 1.
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